WO2009033900A2 - Procédé de purification de silicium polycristallin - Google Patents

Procédé de purification de silicium polycristallin Download PDF

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Publication number
WO2009033900A2
WO2009033900A2 PCT/EP2008/060423 EP2008060423W WO2009033900A2 WO 2009033900 A2 WO2009033900 A2 WO 2009033900A2 EP 2008060423 W EP2008060423 W EP 2008060423W WO 2009033900 A2 WO2009033900 A2 WO 2009033900A2
Authority
WO
WIPO (PCT)
Prior art keywords
cleaning
acid
main
silicon
polycrystalline silicon
Prior art date
Application number
PCT/EP2008/060423
Other languages
German (de)
English (en)
Other versions
WO2009033900A3 (fr
Inventor
Hanns Wochner
Christian Gossmann
Herbert Lindner
Original Assignee
Wacker Chemie Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Priority to EP08787019A priority Critical patent/EP2178794B1/fr
Priority to DE502008003128T priority patent/DE502008003128D1/de
Priority to AT08787019T priority patent/ATE504545T1/de
Priority to US12/674,299 priority patent/US20110186087A1/en
Priority to JP2010521388A priority patent/JP5254335B2/ja
Priority to CA2706386A priority patent/CA2706386C/fr
Priority to CN200880103893A priority patent/CN101784477A/zh
Priority to KR1020107003869A priority patent/KR101231015B1/ko
Publication of WO2009033900A2 publication Critical patent/WO2009033900A2/fr
Publication of WO2009033900A3 publication Critical patent/WO2009033900A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/037—Purification

Definitions

  • the invention relates to a method for purifying polycrystalline silicon without hydrochloric acid and without hydrogen peroxide.
  • Silicon compounds such as trichlorosilane. It falls polycrystalline in the form of rods with typical diameters of 70 to 300 mm and lengths of 500 to 2500 mm. A large part of the bars is used for the production of crucible-pulled single crystals, of ribbons and foils or for the production of polycrystalline solar cell base material. Since these products are made from high purity, molten silicon, it is necessary to use solid silicon melt in crucibles. In order to make this process as effective as possible, large-volume, massive silicon pieces, such as the mentioned polycrystalline rod, must be crushed before melting. This is usually always associated with a surface contamination of the semiconductor material, because the crushing with metallic crushing tools, such as jaw or roll crushers, hammering or chiselling takes place. These impurities consist for example of Metallcarbid-, Diamantruckterrorism and metallic impurities.
  • the contamination by metal atoms is to be regarded as critical, as they can change the electrical properties of the semiconductor material in a harmful way. If the semiconductor material to be comminuted, as hitherto predominantly conventional, is comminuted with mechanical tools, such as, for example, steel crushers, the fragments must be subjected to surface cleaning before melting.
  • metal particles (1) of metal carbide residue do not only get from the abrasion of the crushers or diamond particles from the abrasion of saw blades on the surface of the polysilicon the surface (2), but also into the native oxide layer (3) and in the silicon lattice (4).
  • JP 06 02 10 34 discloses a cleaning solution for semiconductor material.
  • the cleaning solution is composed of water, 30 to 50% HNO3 and 0.1 to 1% HF.
  • JP 051-54466 describes a purification process using hydrofluoric acid and nitric acid. The remaining iron concentration in this process is no longer sufficient according to today's requirements on the purity of polysilicon.
  • EP 0905796 describes a cleaning process consisting of a pre-cleaning by means of a mixture consisting of HF / HC1 / H 2 O 2 of a main cleaning by means of HF / HNO 3 and a subsequent hydrophilization of the silicon surface by HCl / H 2 O 2 .
  • the metal particles are strongly attacked by the acid mixture in the pre-cleaning. This leaves metal carbide residues that are largely dissolved in HF / HNO3 main cleaning.
  • a disadvantage of this method are the exhaust gases occurring.
  • gaseous chlorine, HF and HCl occur during the pre-cleaning, while nitrogen oxides and HF are used for the main cleaning and chlorine gas is used for the hydrophilization.
  • the exhaust gas streams from the pre-cleaning / hydrophilization must not be disposed of via a common exhaust gas disposal system.
  • Aqua regia is already destroying plastics in small quantities, such as polypropylene (PP) or polyethylene (PE). This has the consequence that two completely separate systems for the disposal of the exhaust gases are necessary.
  • the exhaust gases from the pre-treatment and the hydrophilization must be disposed of in a chlorine scrubber, the exhaust gases of the main cleaning in a nitrogen oxide scrubber.
  • the object of the invention was to provide a process for the purification of polysilicon in which the acid consumption is significantly lower and the problems described in the exhaust gas disposal do not occur.
  • the invention relates to a method for purifying polysilicon comprising the steps a.) Pre-cleaning in at least one stage with an oxidizing cleaning solution containing hydrofluoric acid, nitric acid and hexafluorosilicic acid, b.) Main cleaning in a further step with a cleaning solution containing nitric acid and hydrofluoric acid, c .) Hydrophilization in a further stage with an oxidizing cleaning solution.
  • Hydrofluoric acid and especially of hexafluorosilicic acid is surprisingly not impaired in a dilute HNO 3 solution.
  • the pre-cleaning can be carried out at temperatures of 0 to 60 0 C.
  • the pre-cleaning is done at a temperature of 10 to 40 0 C, more preferably at 20 to 30 0 C.
  • the hydrophilization can take place in an aqueous ozone solution, without the presence of hydrogen peroxide.
  • the exhaust gases can all be disposed of together via a nitrogen oxide scrubber.
  • the pre-purification and the main purification can take place in separate acid cycles. In each case, fresh cleaning solutions are prepared for the individual steps. The necessary
  • Acid concentrations are specifically adjusted by a subsequent dosing with hydrofluoric acid and nitric acid.
  • this takes place in the form of a cascade between the pre- and main cleaning.
  • the waste acid resulting from the main purification containing HF, HNO 3 / HNO 2 and H 2 SiF 6 is used again in the pre-cleaning.
  • the metal analyzes on the purified poly-break were carried out as follows:
  • the acid was collected in a Teflon beaker.
  • Example 1 Inductively coupled ion plasma atomic emission spectroscope from Spectro. The measured values were used to calculate the metal content of the poly surface.
  • ICP-AES Inductively coupled ion plasma atomic emission spectroscope from Spectro.
  • EP 0905796 for pre-cleaning a mixture consisting of HF / HC1 / H 2 O 2 used for the main cleaning HF / HNO3 and subsequent hydrophilization of the silicon surface
  • Example 2 The procedure was analogous to Example 1. The pre-cleaning and the main cleaning are linked. The acid from the main cleaning flows after the main cleaning in the pre-cleaning and is used there for pre-cleaning. To adjust any deviating acid concentrations, the required acid can be added as needed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un procédé permettant de purifier du silicium polycristallin sans acide chlorhydrique et sans peroxyde d'hydrogène.
PCT/EP2008/060423 2007-08-22 2008-08-08 Procédé de purification de silicium polycristallin WO2009033900A2 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP08787019A EP2178794B1 (fr) 2007-08-22 2008-08-08 Procédé de purification de silicium polycristallin
DE502008003128T DE502008003128D1 (de) 2007-08-22 2008-08-08 Verfahren zum reinigen von polykristallinem silicium
AT08787019T ATE504545T1 (de) 2007-08-22 2008-08-08 Verfahren zum reinigen von polykristallinem silicium
US12/674,299 US20110186087A1 (en) 2007-08-22 2008-08-08 Process for purifying polycrystalline silicon
JP2010521388A JP5254335B2 (ja) 2007-08-22 2008-08-08 多結晶シリコンの清浄化方法
CA2706386A CA2706386C (fr) 2007-08-22 2008-08-08 Procede de purification de silicium polycristallin
CN200880103893A CN101784477A (zh) 2007-08-22 2008-08-08 纯化多晶硅的方法
KR1020107003869A KR101231015B1 (ko) 2007-08-22 2008-08-08 다결정 실리콘 정제 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007039626A DE102007039626A1 (de) 2007-08-22 2007-08-22 Verfahren zum Reinigen von polykristallinem Silicium
DE102007039626.2 2007-08-22

Publications (2)

Publication Number Publication Date
WO2009033900A2 true WO2009033900A2 (fr) 2009-03-19
WO2009033900A3 WO2009033900A3 (fr) 2010-03-04

Family

ID=40280116

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/060423 WO2009033900A2 (fr) 2007-08-22 2008-08-08 Procédé de purification de silicium polycristallin

Country Status (9)

Country Link
US (1) US20110186087A1 (fr)
EP (1) EP2178794B1 (fr)
JP (1) JP5254335B2 (fr)
KR (1) KR101231015B1 (fr)
CN (2) CN104150488A (fr)
AT (1) ATE504545T1 (fr)
CA (1) CA2706386C (fr)
DE (2) DE102007039626A1 (fr)
WO (1) WO2009033900A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120175613A1 (en) * 2009-09-16 2012-07-12 Shin-Etsu Chemical Co., Ltd. Polycrystalline silicon mass and process for producing polycrystalline silicon mass

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009045700A1 (de) 2009-10-01 2011-04-14 M + S Solution Gmbh Verfahren zum Zerkleinern einer aus Polysilizium hergestellten Stange
DE102011080105A1 (de) * 2011-07-29 2013-01-31 Wacker Chemie Ag Verfahren zur Reinigung von polykristallinen Siliciumbruchstücken
CN102306687B (zh) * 2011-09-28 2012-12-05 湖南红太阳新能源科技有限公司 一种晶体硅太阳能电池pecvd彩虹片返工方法
JP6329909B2 (ja) * 2011-12-28 2018-05-23 インテグリス・インコーポレーテッド 窒化チタンを選択的にエッチングするための組成物および方法
DE102012200992A1 (de) 2012-01-24 2013-07-25 Wacker Chemie Ag Dotierstoffarmes polykristallines Siliciumstück
JP5910226B2 (ja) * 2012-03-26 2016-04-27 栗田工業株式会社 微粒子の洗浄方法
US11498840B2 (en) 2018-03-28 2022-11-15 Tokuyama Corporation Crushed polycrystalline silicon lumps and method for producing same
KR20240034859A (ko) * 2020-08-27 2024-03-14 가부시키가이샤 도쿠야마 다결정 실리콘 파쇄괴
TW202239817A (zh) 2021-01-15 2022-10-16 日商味之素股份有限公司 負型感光性樹脂組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548504A2 (fr) * 1991-10-29 1993-06-30 HI-SILICON Co., Ltd. Procédé de nettoyage d'une masse de silicium
DE19529518A1 (de) * 1994-08-10 1996-02-15 Tokuyama Corp Polykristallines Silizium und Verfahren zu dessen Herstellung
EP0905796A1 (fr) * 1997-09-19 1999-03-31 Wacker-Chemie GmbH Silicium polycristallin
EP1894887A2 (fr) * 2006-08-31 2008-03-05 Wacker Chemie AG Procédé de traitement d'une solution corrosive, formée durant la production de silicium à haute pureté
WO2009024478A2 (fr) * 2007-08-22 2009-02-26 Wacker Chemie Ag Procédé de purification de silicium polycristallin

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US3968640A (en) 1974-09-16 1976-07-13 Hughes Aircraft Company Digital watch with elastomer housing block and flexible printed circuitry
JPH0621034A (ja) 1992-07-02 1994-01-28 Nec Kyushu Ltd 半導体基板の洗浄液
US5445679A (en) * 1992-12-23 1995-08-29 Memc Electronic Materials, Inc. Cleaning of polycrystalline silicon for charging into a Czochralski growing process
US5516730A (en) * 1994-08-26 1996-05-14 Memc Electronic Materials, Inc. Pre-thermal treatment cleaning process of wafers
US6833084B2 (en) * 1999-04-05 2004-12-21 Micron Technology, Inc. Etching compositions
SG92720A1 (en) * 1999-07-14 2002-11-19 Nisso Engineering Co Ltd Method and apparatus for etching silicon
DE10036691A1 (de) * 2000-07-27 2002-02-14 Wacker Siltronic Halbleitermat Verfahren zur chemischen Behandlung von Halbleiterscheiben
US7507670B2 (en) * 2004-12-23 2009-03-24 Lam Research Corporation Silicon electrode assembly surface decontamination by acidic solution
JP4817291B2 (ja) * 2005-10-25 2011-11-16 Ｏｋｉセミコンダクタ株式会社 半導体ウェハの製造方法
CN1851885A (zh) * 2006-04-28 2006-10-25 友达光电股份有限公司 湿蚀刻后的清洗方法及应用其的薄膜晶体管形成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548504A2 (fr) * 1991-10-29 1993-06-30 HI-SILICON Co., Ltd. Procédé de nettoyage d'une masse de silicium
DE19529518A1 (de) * 1994-08-10 1996-02-15 Tokuyama Corp Polykristallines Silizium und Verfahren zu dessen Herstellung
EP0905796A1 (fr) * 1997-09-19 1999-03-31 Wacker-Chemie GmbH Silicium polycristallin
EP1894887A2 (fr) * 2006-08-31 2008-03-05 Wacker Chemie AG Procédé de traitement d'une solution corrosive, formée durant la production de silicium à haute pureté
WO2009024478A2 (fr) * 2007-08-22 2009-02-26 Wacker Chemie Ag Procédé de purification de silicium polycristallin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120175613A1 (en) * 2009-09-16 2012-07-12 Shin-Etsu Chemical Co., Ltd. Polycrystalline silicon mass and process for producing polycrystalline silicon mass
US11440804B2 (en) 2009-09-16 2022-09-13 Shin-Etsu Chemical Co., Ltd. Process for producing polycrystalline silicon mass

Also Published As

Publication number Publication date
CN101784477A (zh) 2010-07-21
ATE504545T1 (de) 2011-04-15
US20110186087A1 (en) 2011-08-04
EP2178794A2 (fr) 2010-04-28
JP5254335B2 (ja) 2013-08-07
CN104150488A (zh) 2014-11-19
WO2009033900A3 (fr) 2010-03-04
DE502008003128D1 (de) 2011-05-19
CA2706386A1 (fr) 2009-03-19
DE102007039626A1 (de) 2009-02-26
CA2706386C (fr) 2012-03-06
KR20100047271A (ko) 2010-05-07
JP2010536698A (ja) 2010-12-02
KR101231015B1 (ko) 2013-02-07
EP2178794B1 (fr) 2011-04-06

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